KR930002235B1 - Carbon black product and rubber compositions containing same - Google Patents

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Description

Carbon black products and rubber compositions containing them

The present invention relates to improved modified carbon black products, rubber compositions containing such products and methods of improving the processability and / or reducing the viscosity of uncured rubber compositions. More particularly, the present invention relates to modified carbon black products that, when incorporated into rubber formulations, reduce the viscosity and hysteresis of the rubber without adversely affecting the tensile strength and modulus properties of the rubber.

Rubber compositions are generally known to be blended or "mixed" with various other materials before they are cured and / or used. Some of these added materials improve the properties of the final product, while others are uncured. Improve processability of the composition. In some cases, both effects may be obtained. It is also known that many of the organic and inorganic chemicals, pigments, and other substances used as such may interact in various ways, leading to desirable or detrimental results. Rubber processing and the materials used therein are described in more detail in the following literature: Encyclopedia of polymer science and technology, published by John Wiley and Sons, New York (1970), in particular Vol. 12, page 280 alc The Vanderbilt Rubber Handbook, RT Vanderbilt Company, Norwalk, Connecticut, 06855 (1968), in particular Sections 6, 7, 8, 9 and 11.

Vulcanizers, plasticizers, extenders, fillers, pigments and the like can generally be incorporated into vulcanizable rubber compositions so that the rubber can be cured or vulcanized in a mold to form useful products. Occasionally, it is necessary to include a processing aid in a rubber compound before molding and curing. These processing aids are mainly used to improve the mixing of the components of the rubber compound, the flowability of the rubber during processing, and the mold or mill release properties of the rubber without adversely affecting the properties of the cured rubber.

Carbon blacks are used in rubber formulations and their properties and combinations of properties vary widely. In rubber formulations, carbon black is used as reinforcing filler. Many carbon blacks of channel and furnace type with different properties have been used because they give various desirable properties to rubber. Among these many properties found in rubber are resistance to oxidation or aging.

Benzofurazine oxides and their homologues and isomers are known compounds, many of which have been described and their manufacturing processes are known. Kaufman et al., "Chemical Reviews", Vol. 59, page 429 and following (1959) and Mallory et al., Organic Synthesis collective Vol. IV, pp. 74 and 75, John Wiley and Sons, Now York (1963). In addition, processes for preparing various types of furazane oxides are described in the following US patents: US Pat. No. 4,185,018 (Fah); US Pat. No. 3,528,098 to Shaw; And US Pat. No. 2,424,199 to Ter Horst. In the foregoing description of furazane oxides and related compounds, it should be noted that the nomenclature used for these compounds is inconsistent, in part due to the uncertainty of their structure and major isomeric forms. For example, they have been described as furazane oxides, as orthodinitroso benzene or di (nitrile oxide), isobenzofuroxane, benzofuroxane, benzofurazane-N-oxide and benzofurazane oxide. The latter terminology is believed to be a modern and preferred nomenclature, which will be used in this specification and the appended claims.

The study of furazane oxide and related compounds in rubber has been reported. See, for example, Rehner and Flory, Industrial and Engineering Chemistry, Vol. 38, page 500 et sec, describes that ortho dinitrosobenzene does not act as a vulcanizing agent in butyl rubber. In contrast, para isomers are said to be very active.

U.S. Patent No. 3,931,121 (Davis et al.) Describes the curing of elastomers using poly (chloronitroso) compounds. U.S. Patent No. 3,93l, 106 (Crosby et al.) Describes the use of dinitrile oxides (generated from furazane in the same reaction system) in rubber cross-linking. British Patent 1,586,861 describes the use of organic compounds that are sources of six-membered aromatic cyclic adjacent nitroso groups for modifying polymeric materials containing carbon-carbon unsaturations. Examples of such polymeric materials are polybutadiene, styrene-butadiene copolymers, butyl rubber, natural rubber and EPDM rubber. The polymeric material may contain fillers such as carbon black and fumed silica. Benzoprazan oxide is an example of a source for adjacent nitroso groups.

US Patent No. 2,974,120 (Miller) describes the use of non-aromatic furoxanes as antioxidants and antidegradants in rubber. US Patent No. 2,905,582 (Coleman et al.) Discloses the use of a nitroso compound comprising a dinitroso compound in which the nitroso group is on non-adjacent carbon in a method of bonding a polyurethane resin to rubber bodies. Described. Morita proposed the use of N, 4-dinitroso-N-methylaniline as an active chemical promoter for carbon black fortification of IIR, NR and SBR [Rubber Chemistry and Technology, Vol. 49, page 1019 and Following (1976). Tanaka et al. Described the study of nitroso benzene in rubber in which chain breaks are observed (Kogyo Kagaku Zasshi 74 (8), page 1701-6 (1971)).

Carbon black and aromatic furazane in an improved process by preforming carbon black and a carbon black product consisting of at least about 10% by weight, based on the weight of carbon black, of at least one aromatic furazane oxide of substructure (I) It has been found that oxides can be incorporated into natural and synthetic rubber compositions.

(Wherein carboatoms are part of a single fused aromatic ring).

The carbon black products described above are particularly useful for incorporating carbon black and furazane oxide in uncured rubber compositions of one or more rubbers with unsaturated carbon chains. Uncured rubber compositions incorporating the carbon black product of the present invention generally exhibit other beneficial properties such as reduced viscosity and improved processability and enhanced strength upon curing. In addition, the carbon black products of the present invention do not have the unique strong odor of furazane oxide, which facilitates the handling and storage of these materials.

The carbon black product of the present invention can be prepared by mixing carbon black having a surface area (EMSA) of about 20 m ² / g or more with a preferred amount of aromatic furazane oxide, and optionally converting the mixture into pellet form. You can.

As another aspect of the invention, at least one rubber having an unsaturated carbon chain; And a small amount of carbon black having a surface area of at least 20 m ² / g and at least one aromatic furazane oxide of the following partial structural formula (I) of about 10% by weight or less based on the weight of the carbon black. Filled vulcanized rubbers made by vulcanizing a composition of carbon black products improve carbon black interaction, hysteresis, modulus, compression set and resiliency.

Wherein the carbon atom is part of a single fused aromatic ring.

Rubber products made from vulcanized rubber such as timers, hose belts, treads, sidewalls and the like and parts thereof are within the scope of the present invention as well as methods for reducing rolling resistance and running temperature of such tires, for example.

The carbon black products of the present invention contain commercially available carbon blacks having a surface area (EMSA) of 20 m ² / g or more, preferably 35 m ² / g to 200 m ² / g or more, which is commercially available. Surface area values used in the present invention are those measured according to ASTM test D-1765 using the cetyltrimethylammonium bromide (CTAB) method. Carbon black with less surface area, such as thermal carbon black, does not yield desirable results. Among the useful carbon blacks are furnace black, channel black and lamp black. More specifically, examples of carbon black include super abrasion furnace (SAF) black, high abrasion furnace (HAF) black, fast extrusion furnace (FEF) black, fine Fine furnace (FF) black, intermediate super abrasion furnace (ISAF) black, semi-reinforcing furnace (SRF) black, medium procesing channel black, severe There are hard processing channel blacks and conducting channel blacks.

Other carbon blacks that may be used include acetylene black. Mixtures of two or more of these blacks may be used to prepare the carbon black product of the present invention. Representative values for the surface area of useful carbon blacks are shown in Table 1 below.

TABLE 1

The carbon blacks used in the preparation of the carbon black products of the present invention may be in pelletized form or non-pelletized agglomerates. Preferably, for more uniform mixing, unpelleted carbon black is preferred for producing the carbon black product of the present invention.

Prepared by mixing the carbon black of the carbon black product of the present invention with one or more preferred amounts of furazane oxide. Furazane oxide used in the present invention is a fused aromatic. That is, they have an aromatic ring fused to an N-oxidized heterocyclic furazane ring. They have the following partial structural formula (I).

Wherein the carbon atom is part of a fused single aromatic ring

The aromatic ring may be carbocyclic, such as a benzene ring, or may be heterocyclic, such as a pyridine ring. This may be the only addition ring in the furazane compound or may be part of a bound or fused ring system. Both carbon atoms of partial structure (I) must be part of the same aromatic ring.

Preferred examples of furazine oxides falling within the range of structural formula (I) useful for preparing the carbon black product of the present invention include compounds that can be represented by (V) in general formula (II).

Wherein none of the cyclic positions are substituted or one or both of the cyclic positions are lower hydrocarbyl, halogen, hydroxyl, lower hydrocarbyloxy, lower hydrocarbylthio, lower hydrocarbyl carbonyl, carbonyl lower And may be substituted with hydrocarbyloxy, nitro, amino or amine groups, Y being a bonding atom or a bonding group. Lower hydrocarbyl herein refers to a group containing carbon and oxygen having up to 8 carbon atoms such as methyl, ethyl, butyl, pentyl, heptyl, octyl (all isomers). Binding atoms or bonding groups Y include ethers, thioethers, sulfoxides, sulfones, amine methylenes and the like (including single covalent bonds such as those derived from biphenyls) and other binding groups are described in US Pat. Cited in the literature). Hydrocarbyloxa, hydrocarbylthia and mixed hydrocarbyloxythia substituents are also possible, where the hydrocarbyl group is typically a lower alkylene moiety. These are sometimes made from glycols, dithiols, epoxides and epi-sulfides. Sometimes, furazane oxide is benzofurazane oxide of formula (II).

Wherein none of the positions on the ring are substituted or one or two of the positions on the ring are lower hydrocarbyl, halogen, lower hydrocarbyloxy, lower hydrocarbylthio, lower hydrocarbyl carbonyl, carbonyl lower hydrocarbyloxy, It may be substituted with nitro, amine or amino group. Typically, the furazane oxide is benzofurazane oxide or its methyl or methoxy homologue.

Methods for the preparation, purification and handling of these compounds are known in the art as described in the references cited above. The preparation of halogenated benzofurazane oxides and other substituted derivatives is described by Boulton et al, J. Chem. Soc. (1965) 5958. Benzotri (furazane oxide) can be prepared according to the methods described in Banley and Case, Tetrohedron, 3 (1958) 113. Some of these furazane oxides, especially those containing relatively large amounts of nitrogen and oxygen, such as benzotri (furazane oxide) and 4,6-di (nitro) benzofurazane oxide, are susceptible to rapid decomposition to the point of explosion. ; It will be appreciated that it can be physiologically active to all varying degrees. Therefore, care must be taken in their handling and use.

Carbon black and furazane oxide are mixed in a suitable manner. For example, in the case where the carbon black is a non-pelletized agglomerate, the carbon black and furazane oxide are added to a container, heated to a temperature above the melting point of the furazane oxide, and then the carbon black and furazane oxide are mixed thoroughly. Can be rotated to When the mixing process is complete, the resulting mixture is heated in an oven to obtain a homogeneous mixture of carbon black and furazane oxide. The nature of the bond between carbon black and furazane oxide is not known for certain, and the bond can be a physical or chemical bond or a mixture of physical and chemical bonds.

If the carbon black product of the present invention is desired to have a pelletized form, the carbon black and furazane oxide (optionally, together with the liquid substance normally used in the pelletization operation) are mixed and then the desired size under pelletizing conditions. Formed into pellets and then heated. Pelletization aids such as molasses and the like commonly used can also be used in the preparation of the carbon black products of the invention.

As mentioned, whether the carbon black product of the present invention is produced in agglomerated or pelletized form, the product formed by mixing carbon black and furazane oxide is less than or equal to the decomposition temperature of a particular furazane oxide in a suitable apparatus. Heat to elevated temperature. In general, a temperature of about 100 to 150 ° C. is suitable, and the heating time may be about 1 hour or more depending on the particular temperature selected.

The amount of furazane oxide combined with the carbon black to form the carbon black product of the present invention can vary widely. In general, the amount of furazane oxide has been found to be about 10% by weight or less, based on the weight of the carbon black, to be sufficient to provide a carbon black product having the desired properties used in the preparation of vulcanized rubber having the desired properties. .

The carbon black products of the present invention are useful for improving the properties of rubber compositions, as described above. Therefore, the carbon black product of the present invention is added and incorporated into the uncured, unvulcanized-rubber composition. In some cases, the rubber composition contains a curing agent (system) and can therefore be cured or vulcanized. In other cases, the carbon black product of the present invention is incorporated because the rubber composition is an intermediate composition to which the curing system is to be added or the high casting is used without the addition of a curing agent for applications such as sealants, caulks, adhesives, and the like. The resulting rubber composition does not contain a curing agent. In any case, the present invention encompasses the uncured-rubber composition containing the carbon black product of the present invention, whether the rubber composition further contains a curing agent, and whether the rubber composition is an intermediate to which the curing agent is to be added. .

When a curing agent is used, the curing agent is a conventional form such as a sulfur- or peroxide-based curing system. Curing agents are used in conventional amounts and incorporated into the uncured compositions of the present invention by known methods and processes. Fillers (pigments other than carbon black) can be used and are often used as known to those skilled in the art. Representative fillers include glass, silica, talc and similar finely divided minerals.

As used herein, the term "rubber" includes not only natural rubber but also synthetic rubber, and the rubber composition of the present invention includes natural rubber; And rubbery polymers prepared by polymerizing aliphatic conjugated diolefins, in particular diolefins containing 4 to 8 carbon atoms per molecule, such as butadiene, isoprene, pentadiene and the like or copolymers of such dienes. The rubber used in the uncured composition of the present invention preferably has an unsaturated carbon chain. That is, their polymeric backbones contain significant amounts of unsaturation compared to pendant or vinyl saturations found in some other types of rubber. Typically, the chains of such unsaturated rubbers have at least about 20% carbon-to-carbon bonds as unsaturated bonds. The properties of rubber as having an unsaturated carbon chain are well known in the art as described in ANSI / ASTM Standard D 1418-79A, which refers to unsaturated chain rubber as R rubber. The R rubber class includes several synthetic rubbers at least partially derived from natural rubbers and diolefins. Class R rubbers that may be used in the compositions of the present invention are as follows:

ABR-acrylate-butadiene

BIIR-Bromo-Isobutene-Isoprene

BR-Butadiene

CIIR-Chloro-isobutene-isoprene

CR-chloroprene

IIR-isobutene-isoprene

IR-isoprene, synthetic

NBR-nitrile-butadiene

NCR-nitrile-chloroprene

NIR-nitrile-isoprene

NR-natural rubber

PBR-pyridine-butadiene

PSBR-pyridine-styrene-butadiene

SBR-Styrene-Butadiene

SCR-styrene-chloroprene

SIR-styrene-isoprene rubber

Among them, NR, IR, BR, SBR, CR, CIIR, NIR or a mixture of two or more thereof are commonly used. Many compositions are made wherein the rubber is at least about 50% NR, SBR or a mixture thereof. Compositions containing only NR as the rubber part are often used. In the present invention, NR includes hevea and guayule rubbers as well as mixtures thereof.

In addition, the rubber compositions of the present invention may contain materials used in conventional rubber formulations such as antioxidants, accelerators, retarders, promoters, etc., in addition to the curing systems and fillers described above. However, it will be appreciated that these materials can sometimes be selected carefully because they can interact with the necessary furazane oxide.

The rubber of another aspect of the present invention with respect to vulcanized rubber (ie cured material) is about the same as that described above.

The vulcanized rubbers of the present invention may also contain fillers in conventional forms such as clay, talc, pyrophyllite, silica and other inorganic finely divided materials. In addition, the vulcanized rubber of the present invention contains conventional curing systems and curing agents such as sulfur, antioxidants, accelerators, retarders, coupling agents, accelerators and the like.

Vulcanizable compositions containing the carbon black products of the present invention can be prepared by conventional methods using various types of mills, blendies and mixers known in the art. The curing composition can be prepared and cured in the same manner. Usually, the amount of furazane oxide incorporated into the vulcanizable composition as part of the carbon black product is an amount that improves properties, such as an amount that improves the processability of the composition. Processability relates to the ease and efficiency in mixing, grinding and handling the rubber composition in the unvulcanized state, that is, in the uncured state. Processability includes viscosity and often includes the rate and efficiency at which various other components are dispersed in the rubber. A similar amount is used in the curing composition to improve vulcanizing rubber properties such as filler interaction, modulus, elasticity, hysteresis, rolling resistance, running temperature and the like. Typically, the amount that improves this property of furazan oxide is about 0.1 to 10 parts by weight per 100 parts by weight of rubber (phr). Often, furazane oxide is incorporated in amounts of 0.5 to 5 phr.

The temperature used to formulate the rubber composition of the present invention is the temperature normally used in the art and is generally at least about 140 ° C. depending on the particular elastomer processed. More broadly, the formulation may be at about 140 ^° to 220 ° C. Due to the shear stress associated with the formulation of the rubber composition, the formulation process is exothermic and high temperatures are common. As mentioned above, fillers, accelerators, curing agents and other conventional rubber additives are also sometimes contained in these uncured mixtures in conventional amounts.

The vulcanized rubber of the present invention is prepared by curing a composition containing a carbon black product under the conditions of temperature and time commonly used in the art, and the present invention does not vary significantly with these curing parameters. Typically, the rubber carbon black product and other fillers (or pigments) are mixed and then the mixture is cured. Other mixing sequences may be used, but the rubber and carbon black products must be homogenized prior to vulcanization.

Among the desirable and beneficial properties exhibited by the inventive rubber compositions made from the carbon black products of the invention are improved processability, increased raw strength and generally reduced viscosity. Compositions containing significant amounts (> 50%) of NR, IR or CR exhibit improved processability. Improved processability of uncured rubber formulations is desirable because it allows to save energy and time during compounding and subsequent processing of rubber by methods such as calendering, milling, remilling, extraction, and the like. . These savings are important for current short time and price increases. In general, processability is a generic term used to describe reduced viscosity and / or high raw strength as developed in the compositions of the present invention. To date, reducing the viscosity of an uncured composition has often been known to result in reduced raw strength. Likewise, increasing the raw strength has been known to increase the viscosity. Obtaining a decrease in viscosity with an increase in raw strength is a particularly preferred feature of the compositions of the present invention.

In general, NR, IR and CR containing compositions exhibit a decrease in viscosity of about 20 Mooney units with an increase in raw strength of about 20 to 100 psi for about 0.5 to 1.5 phr of furazane oxide. For example, a similar content of furazane oxide in synthetic rubber such as SBR increases the peak raw strength by about 5 to 50 psi while increasing the Mooney viscosity by about 10 units. With a high content of furazane oxide (eg, 2 to 5 phr), the peak of viscosity reduction can be reached with the liquefaction of NR and IR. These liquid rubbers are useful in sealants and as processing aids that are blended with other forms of rubber to help plasticize the rubber. Liquid rubbers, also known as depolymerized rubbers (DPRs), are well known in the art and need not be described further herein. Viscosity decreases observed in the compositions of the present invention are sometimes found to be noticed by the inclusion of antioxidants and materials such as carbon black, which are believed to interact and trap the polymer free radicals prior to their cross-linking. . Therefore, maximum viscosity reduction can usually be achieved by adjusting the concentration of furazan oxide, carbon black, and antioxidant or radical trapping material (filler) in a given rubber composition.

EXAMPLE

The following non-limiting examples illustrate the practice of the present invention and include the best methods currently known. As in the specification and claims, in these examples all parts and percentages are parts by weight and percentages unless otherwise indicated and the temperature is in degrees Celsius. Unless stated otherwise, conventional rubber compounding materials, conditions, temperatures, processes and evaluation methods are used. Examples 1-5 illustrate the preparation of the carbon black product of the present invention, and Examples A and B illustrate several of the various rubber compositions of the present invention using the carbon black product of the present invention.

Example 1

A mixture of 150 parts of HAF unpelleted carbon black (ASTM 1765 Designation N-339) and 6.2 parts (4% by weight) of benzofurazane oxide was prepared in a 28-oz beverage bottle and the bottle was kept at 80 ° C. Spin for about 16 hours. The bottle is then stored for another 4 hours in an oven maintained at 120 ° C. The resulting blend is a homogeneous mixture of furazane oxide and carbon black that does not smell of unique furazane oxide.

Example 2

A mixture of about 100 parts of ISAF carbon black (N-220) and 5 parts of benzofurazane oxide is prepared in a 28-oz beverage bottle. After the bottle is rotated for about 16 hours in a water bath maintained at 80 ° C., the bottle is stored at a temperature of 125 ° C. for about 4 hours in a static oven. The desired carbon black product is obtained.

Example 3

A mixture of about 100 parts of ISAF carbon black (N-220) and 5 parts of 6-methylbenzofurazane oxide (MBFO) is prepared in a 28-oz beverage bottle. After rotating the bottle for about 16 hours in a water bath maintained at 80 ° C., the bottle is stored at 125 ° C. for about 4 hours in a static oven. The desired carbon black product is obtained.

Example 4

The method of Example 1 is repeated except that the carbon black used is SRF black, N-660.

Example 5

The method of Example 2 is repeated except that the carbon black used is SAF black, N-110.

[Master batch production]

In the examples below, a hermetic mixer such as a Brabender or a small Banbury mixer is used. The usual method is to add the various materials occasionally in small portions to the mixer and continue mixing for the indicated time. It is then further added to the master batch thus produced and then mixed. The standard method is according to the following table:

Then the uncured master batches are immediately combined and sheeted to 60 gauge on a small set of dual roll mills. Measure the Mooney viscosity at 100 ^o using a large rotor at 4 minute intervals. This process is used to make master batches from Hevea and SBR (trade name: Duradene, The Firestone Trie & Rubber Company, Akron, Ohio, USA).

Example A

A SBR-based passenger car tire tread material formulation (control) is prepared containing about 60 phr of HAF carbon black and conventional amounts of zinc oxide, stearic acid and wax antioxidants. A similar formulation is prepared containing 24 phr of the carbon black product of Example 1 (BFO treated) instead of 60 parts of HAF black.

The formulation is cured at about 150 ° C. and the physical properties of both cured formulations are measured. The measurement results are summarized in Table II below.

TABLE II

Example B

A natural rubber (NR) composition (control) is prepared containing about 60 parts ISAF black, about 15 parts Hi-Sil silica and conventional amounts of zinc oxide, an antioxidant. The carbon black products of Examples 2 and 3 were used in place of 60 parts of ISAF black to make two nearly identical compositions. The amount of carbon black product contained in these formulations is an amount sufficient to provide a benzofurazane oxide content of 1 phr. These three formulations are cured at about 150 ° C. and some of the physical properties of the cured formulations are evaluated. The results are summarized in Table III.

TABLE III

(a) the product of Example 2

(b) the product of Example 3

(c) Measured at 4 minute intervals using a large rotor.

As can be seen from Table III, the material containing the carbon black product of the present invention exhibits a reduced Mooney viscosity.

It has also been observed that the use of the carbon black product of the present invention in rubber compositions results in less tear strength compared to rubber compositions containing carbon black and individually added furazane oxide. In other words, the carbon black composition of the present invention is more effective in suppressing the tear strength loss due to the addition of furazane oxide than when carbon black and furazane oxide are separately added to the rubber.

The vulcanizable rubber compositions of the invention produced using the carbon black products of the invention can be molded or molded into the desired form by known methods, and can be used for various applications in which similar compositions are used. For example, it can be used for tire tubes, tire treads, tire casings, shoe soles and heels, raincoats, tablecloths, fluid transfer hoses, belts, printing rolls, printing press covers, engraving plates, battery boxes and the like. It is especially preferable to use it as a tire material.

While the present invention has been described and illustrated herein with respect to particular materials, mechanisms, methods, processes and examples, it will be apparent to those skilled in the art that various modifications, combinations and exchanges can be made within the scope of the invention. It is understood that there is.

Claims (26)

A carbon black product useful in rubber compositions, comprising carbon black having a surface area of at least 20 m ² / g and at least one aromatic furazane oxide of the following substructure (I), based on the weight of the carbon black.

Wherein the carbon atom is part of a single fused aromatic ring. The carbon black product according to claim 1, wherein the furazane oxide is a compound of the following general formulas (II), (III), (IV) or (V).

Wherein none of the cyclic positions are substituted or one or two of the cyclic positions are lower hydrocarbyl, halogen, hydroxyl, lower hydrocarbyloxy, lower hydrocarbylthio, lower hydrocarbyl carbonyl, carbonyl lower hydro May be substituted by carbyloxy, nitro, amine or amino group; Y is a bonding atom or a bonding group. 3. The carbon black product of claim 2, wherein the furazane oxide is a compound of formula II.

Wherein none of the cyclic positions are substituted or one or two of the cyclic positions are lower hydrocarbyl, halogen, hydroxyl, lower hydrocarbyloxy, lower hydrocarbylthio, lower hydrocarbyl carbonyl, carbonyl lower hydro It may be substituted by carbyloxy, nitro, amine or amino group. The carbon black product of claim 1, wherein the furazane oxide is benzofurazane oxide or a methyl or methoxy homolog thereof. The carbon black product of claim 1, wherein the aromatic furazane oxide is adsorbed onto the carbon black. The carbon black product of claim 1 in pelletized form. At least one rubber having an unsaturated carbon chain; And a small amount of carbon black having a surface area of at least 20 m ² / g and a mixture of at least about 10% by weight based on the weight of the carbon black and at least one aromatic furazane oxide of the following substructure (I). An uncured rubber composition consisting of a preformed carbon black product.

Wherein the carbon atom is part of a single fused aromatic ring. 8. The rubber composition of claim 7, wherein the rubber is NR, IR, BR, SBR, CR, CIIR, NIR or a mixture of two or more of these rubbers. 8. The rubber composition of claim 7, wherein the rubber is NR, SBR, or a mixture containing at least about 50% thereof. 8. The rubber composition of claim 7, wherein the furazane oxide is a compound of formula (II), (III), (IV) or (V).

Wherein none of the cyclic positions are substituted or one or two of the cyclic positions are lower hydrocarbyl, halogen, hydroxyl, lower hydrocarbyloxy, lower hydrocarbylthio, lower hydrocarbyl carbonyl, carbonyl lower hydro May be substituted by carbyloxy, nitro, amine or amino group; Y is a bonding atom or a bonding group. The rubber composition of claim 10, wherein the furazane oxide is a compound of formula II.

Wherein none of the cyclic positions are substituted or one or two of the cyclic positions are lower hydrocarbyl, halogen, hydroxyl, lower hydrocarbyloxy, lower hydrocarbylthio, lower hydrocarbyl carbonyl, carbonyl lower hydro It may be substituted by carbyloxy, nitro, amine or amino group. 8. The rubber composition of claim 7, wherein the furazane oxide is benzofurazane oxide or methyl or methoxy homolog thereof. 8. The rubber composition of claim 7, wherein the preformed carbon black product is in pelletized form. An effective amount of a preformed carbon black product consisting of carbon black having a surface area of at least 20 m ² / g and at least one aromatic furazane oxide of the following substructure (I) of about 10% by weight based on the weight of the carbon black, A non-cured rubber composition containing at least one rubber having an unsaturated carbon skeletal chain, thereby improving the processability and / or reducing the viscosity of the rubber composition.

Wherein the carbon atom is part of a single fused aromatic ring. 15. The process of claim 14, wherein the furazane oxide is benzofurazane oxide of formula II.

Wherein none of the cyclic positions 4,5,6 and 7 are substituted or one or two of the cyclic positions 4,5,6 and 7 are lower hydrocarbyl, hydroxyl, halogen, lower hydrocarbyloxy, lower hydro Carbonylthio, lower hydrocarbyl carbonyl, carbonyl lower hydrocarbyloxy, nitro, amine or amino groups, and the remaining positions are substituted with hydrogen atoms. The method of claim 14, wherein the rubber is NR, IR, BR, SBR, CR, CIIR, NIR or a mixture of two or more of these rubbers, wherein a curing agent is present. The method of claim 15, wherein the processability of the NR, SBR or IR, or mixture containing one or more thereof is enhanced. At least one rubber having an unsaturated carbon chain; And a small amount of preliminary effective to improve properties, consisting of carbon black having a surface area of at least 20 m ² / g and at least one aromatic furazane oxide of the following substructure (I) of about 10% by weight or less based on the weight of the carbon black. Filled vulcanized rubber prepared by vulcanizing a composition consisting of a molded carbon black product.

Wherein the carbon atom is part of a single aromatic ring. The vulcanized rubber according to claim 18, wherein the rubber is NR, IR, BR, SBR, CR, CIIR, NIR or a mixture of two or more of these rubbers. The vulcanized rubber according to claim 18, wherein the rubber is NR, SBR or a mixture containing at least about 50% NR, and wherein silica filler is present. The vulcanized rubber according to any one of claims 18 to 20, wherein furazane oxide is a compound of formula (II).

None of the cyclic positions 4,5,6 and 7 is substituted or one or two of the cyclic positions 4,5,6 and 7 are lower hydrocarbyl, hydroxyl, halogen, lower hydrocarbyloxy, lower hydrocarbylthio, Lower hydrocarbylcarbonyl, carbonyl lower hydrocarbyloxy, nitro, amine or amino group. The vulcanized rubber of claim 21 wherein the furazane oxide is benzofurazane oxide or a methyl or methoxy homolog thereof. 20. A tire wherein at least a portion is formed of the vulcanized rubber of claim 18 or 19. A tire formed from the vulcanized rubber of claim 18, wherein at least a portion consists of NR or a mixture containing at least 50% NR. 21. A method of reducing rolling resistance of a tire, comprising forming the tread portion of the tire with the vulcanized rubber of any one of claims 18-20. Filler-interaction of a preformed carbon black product consisting of carbon black having a surface area of at least 20 m ² / g and at least about 10% by weight based on the weight of the carbon black and at least one aromatic furazane oxide of the following substructure (I): A method for improving rubber-filler interaction in filled vulcanized rubber consisting of carbon black filler and at least one rubber having an unsaturated carbon chain, comprising incorporating a small amount effective in improving the action in a vulcanizable composition for making vulcanized rubber. .

Wherein the carbon atom is part of a single aromatic ring.